On subjecting a bulk 2H-PbI2 crystal to vacuum annealing at 500 K followed by a sudden cooling at liquid nitrogentemperature stacking faults are generated that separate distinct layers of nanometricthickness in which different numbers of I–Pb–I atomic layers are bundled together. Suchstructures, containing two, three, four, five etc I–Pb–I atomic layers, behave as quantumwells of different widths. The signature of such a transformation is given by a shift towardshigher energies of the fundamental absorption edge, which is experimentally revealed byspecific anisotropies in the photoluminescence and Raman spectra. The quantumconfining effect is made visible by specific variations of a wide extra-excitonicband (G) at 2.06 eV that originates in the radiative recombination of carriers(electrons and holes), trapped on the surface defects. The excitation spectrum ofthe G band, with p polarized exciting light, reveals a fine structure comprisedof narrow bands at 2.75, 2.64, 2.59 and 2.56 eV, which are associated with thePbI2 quantum wells formed from two, three, four and five I–Pb–I atomic layers of0.7 nm thickness. Regardless of the polarization state of the laser excitinglight of 514.5 nm (2.41 eV), which is close to the band gap energy ofPbI2 (2.52 eV), the Raman scattering on bulk as-grownPbI2 crystals has the character of a resonant process. For p polarizedexciting light, the Raman scattering process on vacuum annealedPbI2 becomes non-resonant. This originates from the quantum well structures generated insidethe crystal, whose band gap energies are higher than the energy of the exciting light.
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